Aqueous emulsion composition

ABSTRACT

An aqueous emulsion composition comprising (A) an aqueous resin emulsion comprising a fluorine-containing polymer and (B) a surfactant of the formula: 
 
R 1 O—(CH 2 CH 2 O) p —(R 2 O) q —R 3    (1) 
 
wherein R 1  is an alkyl group or an alkenyl group, R 2  is an alkylene group, R 3  is a hydrogen atom, an alkyl group or an alkenyl group, p is the number of at least 2, q is the number of at least 1, and p and q are such numbers that the weight ratio of the polyoxyethylene block is from 5 to 80% by weight based on whole molecule, is excellent in stability against impurity and mechanical stability.

TECHNICAL FIELD

The present invention relates to an aqueous emulsion composition whichis excellent in the stability against mechanical impact in the treatmentbath and the stability in the presence of impurity in the treatment bathat the treatment with aqueous resin emulsion, which can maintain highwater- and oil-repellency and its durability.

BACKGROUND ARTS

It is known that a polymer prepared from a polymerizable compound havinga perfluoroalkyl or perfluoroalkenyl group and an acrylate ormethacrylate group is useful as a water- and oil-repellent agent usedfor a textile and woven fabric. Particularly an aqueous dispersionwherein said polymer is dispersed in an aqueous medium with anemulsifier is industrially and widely used.

A water- and oil repellent agent processing bath prepared by dilutingconventional aqueous dispersions, however, often has the problems that aimpurity attached to a processed fabric during a pretreatment stepincorporates into the bath in a treatment step, and then thedispersibility of the aqueous dispersion is deteriorated, emulsionparticles may agglomerate and precipitation may be caused, or thedispersion is broken because of a mechanical impact exerted when atreated fabric enters into the bath or leaves from the bath, emulsionparticles may agglomerate and precipitation may be caused, so that thewater- and oil-repellency performance is deteriorated and the polymerattaches to a roll to give a soiled fabric. That is, the conventionalaqueous dispersions are insufficient in stability against impurity andmechanical stability during treatment step.

Methods having excellent stability against impurity are proposed inJP-A-9-118877, JP-A-9-125051 and JP-A-9-302335, but do not alwaysprovide sufficiently satisfactory stability in connection with varietyof recent water- and oil-repellent treatments.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide an aqueous emulsioncomposition excellent in impurity stability and mechanical stability,and a processing method comprising the same.

The present invention provides an aqueous emulsion compositioncomprising:

-   -   (A) an aqueous resin emulsion comprising        -   a homopolymer or copolymer comprising at least one            polymerizable compound having a perfluoroalkyl or            perfluoroalkenyl group and an acrylate, methacrylate or            alpha-substituted acrylate group, or        -   a copolymer comprising said polymerizable compound and            another compound copolymerizable therewith, and    -   (B) a surfactant of the formula:        R¹O—(CH₂CH₂O)_(p)—(R²O)_(q)—R³   (1)    -   wherein R¹ is an alkyl group having 1 to 22 carbon atoms or an        alkenyl group having 2 to 22 carbon atoms,    -   R² is an alkylene group having at least 3 carbon atoms,    -   R³ is a hydrogen atom, an alkyl group having 1 to 22 carbon        atoms or an alkenyl group having 2 to 22 carbon atoms,    -   p is the number of at least 2,    -   q is the number of at least 1, and    -   p and q are such numbers that the weight ratio of the        polyoxyethylene block is from 5 to 80% by weight based on whole        molecule,        -   wherein the surfactant (B) is added to the aqueous resin            emulsion (A).

MODE FOR CARRYING OUT THE INVENTION

The aqueous resin emulsion is an aqueous emulsion of afluorine-containing polymer.

The fluorine-containing polymer is a homopolymer of afluorine-containing monomer, a copolymer of at least two 2fluorine-containing monomers, or a copolymer of a fluorine-containingmonomer and another polymerizable compound copolymerizable with thefluorine-containing monomer.

The fluorine-containing monomer is a polymerizable compound having aperfluoroalkyl or perfluoroalkenyl group and an acrylate, methacrylateor alpha-substituted acrylate group.

Examples of the polymerizable compound having a perfluoroalkyl orperfluoroalkenyl group and an acrylate, methacrylate oralpha-substituted acrylate group are (meth)acrylate esters representedby the formulas:

-   -   wherein Rf is a perfluoroalkyl group or perfluoroalkenyl group        having 1 to 21 (for example, 3 to 21) carbon atoms, R¹ is        hydrogen or an alkyl group having 1 to 10 carbon atoms,    -   R² is an alkylene group having 1 to 10 carbon atoms,    -   R³ is a hydrogen atom, a methyl group, a fluorine atom, a        chlorine atom, a bromine atom, an iodine atom, a CFX¹X² group        (provided that X¹ and X² are a hydrogen atom, a fluorine atom, a        chlorine atom, a bromine atom or an iodine atom.), a cyano        group, a linear or branched fluoroalkyl group having 1 to 21        carbon atoms, a substituted or unsubstituted benzyl group, or a        substituted or unsubstituted phenyl group,    -   Ar is an aryl group which may have a substituent group, and    -   n is an integer of 1 to 10.

In the above formulas, the Rf group is preferably a perfluoroalkylgroup. The carbon number of the Rf group is from 1 to 21, particularlyfrom 2 to 20, especially from 4 to 16, for example, from 6 to 14. Thecarbon number of the Rf group may be from 1 to 6, particularly from 1 to4. Examples of the Rf group are —CF₃, —CF₂CF₃, —CF₂CF₂CF₃, —CF(CF₃)₂,—CF₂CF₂CF₂CF₃, —CF₂CF(CF₃)₂, —C(CF₃)₃, —(CF₂)₄CF₃, —(CF₂)₂CF(CF₃)₂,—CF₂C(CF₃)₃, —CF(CF₃)CF₂CF₂CF₃, —(CF₂)₅CF₃, —(CF₂)₃CF(CF₃)₂,—(CF₂)₄CF(CF₃)₂, —(CF₂)₇CF₃, —(CF₂)₅CF(CF₃)₂, —(CF₂)₆CF(CF₃)₂ and—(CF₂)₉CF₃.

Specific examples of the polymerizable compound having an acrylate ormethacrylate group are as follows:

In the alpha-substituted acrylate group, examples of thealpha-substituent are a halogen atom, an alkyl group (for example,having 1 to 21 carbon atoms) wherein a hydrogen atom is substituted witha halogen atom (for example, a monofluoromethyl group or difluoromethylgroup), a cyano group, an aromatic group (for example, a substituted orunsubstituted benzyl group, and a substituted or unsubstituted phenylgroup).

Examples of the fluorine-containing polymerizable compound having thealpha-substituted acrylate group are as follows:

wherein Rf is a linear or branched perfluoroalkyl or perfluoroalkenylgroup having 1 to 21 carbon atoms.

The another copolymerizable compound may be various. Examples of theanother copolymerizable compound include:

-   -   (1) acrylic acid and methacrylic acid, and methyl, ethyl, butyl,        isobutyl, t-butyl, propyl, 2-ethylhexyl, hexyl, decyl, lauryl,        stearyl, isobornyl, β-hydroxyethyl, glycidyl, phenyl, benzyl and        4-cyanophenyl esters thereof;    -   (2) vinyl esters of fatty acids such as acetic acid, propionic        acid, caprylic acid, lauric acid and stearic acid;    -   (3) styrene compounds such as styrene, a-methylstyrene and        p-methylstyrene;    -   (4) vinyl and vinylidene halide compounds such as vinyl        fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride and        vinylidene chloride;    -   (5) fatty acid allyl esters such as allyl heptanoate, allyl        caprylate and allyl caproate;    -   (6) vinyl alkyl ketones such as vinyl methyl ketone and vinyl        ethyl ketone;    -   (7) acryl amides such as N-methylacrylamide and        N-methylolmethacrylamide; and    -   (8) dienes such as 2,3-dichloro-1,3-butadiene and isoprene.

A chlorine-containing polymerizable compound (for example, vinylchloride and vinylidene chloride) (for example, in the amount of 1 to50% by weight based on the polymer) is preferably contained as theanother polymerizable compound

The average molecular weight of the fluorine-containing polymer (A) maybe from 1,000 to 10,000,000, for example, from 1,000 to 1,000,000.

The surfactant (B) is a surfactant of the formula:R¹O—(CH₂CH₂O)_(p)—(R²O)_(q)—R³   (1)

-   -   wherein R¹ is an alkyl group having 1 to 22 carbon atoms or an        alkenyl group having 2 to 22 carbon atoms,    -   R² is an alkylene group having at least 3 carbon atoms,    -   R³ is a hydrogen atom, an alkyl group having 1 to 22 carbon        atoms or an alkenyl group having 2 to 22 carbon atoms,    -   p is the number of at least 2,    -   q is the number of at least 1, and    -   p and q are such numbers that the weight ratio of the        polyoxyethylene block is from 5 to 80% by weight based on whole        molecule,

In the surfactant (B), q may be the number of at least 2. That is,—(R²O)_(q)— may form the polyoxyalkylene chain.

The surfactant (B) is a polyoxyethylenealkylene alkyl ether having ahydrophilic polyoxyethylene chain in the molecular center and ahydrophobic oxyalkylene chain (particularly, polyoxyalkylene chain).Examples of the hydrophobic oxyalkylene chain include an oxypropylenechain, an oxybutylene chain and a styrene chain. Among them, theoxypropylene chain is preferable.

Examples of the surfactant (B) include the followings:C₁₀H₂₁O—(CH₂CH₂O)_(p)—(C₃H₆O)_(q)—HC₁₂H₂₅O—(CH₂CH₂O)_(p)—(C₃H₆O)_(q)—HC₁₆H₃₁O—(CH₂CH₂O)_(p)—(C₃H₆O)_(q)—HC₁₆H₃₃O—(CH₂CH₂O)_(p)—(C₃H₆O)_(q)—HC₁₈H₃₇O—(CH₂CH₂O)_(p)—(C₃H₆O)_(q)—HC₁₂H₂₅O—(CH₂CH₂O)_(p)—(C₃H₆O)_(q)—C₁₂H₂₅C₁₆H₃₁O—(CH₂CH₂O)_(p)—(C₃H₆O)_(q)—C₁₆H₃₁C₁₆H₃₃O—(CH₂CH₂O)_(p)—(C₃H₆O)_(q)—C₁₂H₂₅wherein p and q are the same as the above.

The ratio of the polyoxyethylene block may be from 5 to 80% by weight,for example, from 30 to 75% by weight, particularly form 40 to 70% byweight, based on the molecular weight of the surfactant (B) (copolymer).

The average molecular weight of the surfactant (B) is generally from 300to 5,000, for example, from 500 to 3,000.

The surfactant (B) may be used alone or in combination of at least two.The surfactant (B) is added as a protective colloid to the polymerizedaqueous resin emulsion for the purpose of increasing the stability ofthe aqueous resin emulsion after the polymerization. The amount of thesurfactant (B) may be from 0.01 to 30 parts by weight, for example, from1 to 20 parts by weight, based on 100 parts by weight of the polymer.

In addition to the surfactant (B), another surfactant (C) other than thesurfactant (B) can be used. Examples of the surfactant (C) include acationic emulsifier, an anionic emulsifier or a non-ionic emulsifier.The cationic surfactant, the non-ionic emulsifier and a mixture of bothare preferable.

The cationic emulsifier includes dodecyl trimethyl ammonium acetate,trimethyl tetradecyl ammonium chloride, hexadecyl trimethyl ammoniumbromide, trimethyl octadecyl ammonium chloride, (dodecylmethylbenzyl)trimethyl ammonium chloride, benzyl dodecyl dimethyl ammonium chloride,methyl dodecyl di(hydropolyoxyethylene) ammonium chloride, benzyldodecyl di(hydropolyoxyethylene) ammonium chloride andN-[2-(diethylamino)ethyl]oleamide hydrochloride.

The non-ionic emulsifier includes a condensate product of ethylene oxideand hexyl phenol, isooctyl phenol, hexadecanol, oleic acid,alkane(C₁₂-C₁₆) thiol, sorbitan monofatty acid(C₇-C₁₉), alkyl(C₁₂-C₁₈)amine or the like. The amount of the surfactant (C) is from 0.01 to 30parts by weight, for example, from 1 to 20 parts by weight, based on 100parts by weight of the polymer (A).

The composition of the present invention may contain an antifoamingagent depending on the necessity. Particularly when the increase of foamcaused by the containment of the surfactant will be apprehended, it isnecessary to use the antifoaming agent. The antifoaming agent includevarious types for aqueous system and examples of the antifoaming agentinclude lower alcohols such as methanol, ethanol and butanol; higheralcohols such as amyl alcohol, polypropylene glycol and derivativesthereof; oils and fats such as oleic acid, tall oil, mineral oil andsoap; surfactants such as sorbitan fatty acid ester, polyethylene glycolfatty acid ester and Pluronic nonionic surfactant; silicone surfactantssuch as siloxane and silicone resin. These are used alone or incombination. Representatives of commercially available antifoamingagents are B-series such as ADEKANATE B and ADEKANATE B1068 (availablefrom Asahi Denka Co., Ltd.); FOAMASTER DL, NOPCO NXZ, DEFOAMER seriessuch as SN DEFOAMER 113, 325, 308 and 368; DEHYDRAN 1293, DEHYDRAN 1513(available from San Nopco Ltd.); FLOWNON SB-110N, SB-210, 510, 551,AQUALEN 800, 805, AQUALEN 1488 (available from Kyoeisya Chemical Co.,Ltd.); SURFYNOL 104E (acetylene-based antifoaming agent available fromAir Products and Chemicals, Inc.); KS-607A (available from Shin-EtsuChemical Co., Ltd.); FS ANTIFOAM (available from Dow Corning Inc.);BYK-020, 031, 073, W (available from BYK Chemie); DEHYDRAN 981(available from Henkel Japan Co., Ltd.); EPAN-410, 710, 720 (availablefrom Dai-ichi Kogyo Seiyaku Co., Ltd.); TEGO FORMEX Series (availablefrom Tego Goldschmidt); and FOAMLEX-747, TY-10, EP series (availablefrom Nicca Chemical Co., Ltd.). The amount of the antifoaming agent ispreferably from 0.01 to 10% by weigh, more preferably from 0.05 to 5% byweight, based on the aqueous resin emulsion.

In the present invention, an organic solvent may be optionally added forthe purpose of increasing the dispersibility of the polymer. Examples ofthe organic solvent are ketones such as acetone and methyl ethyl ketone;ethylene glycol derivatives such as ethylene glycol and polyethyleneglycol; alkyl ethers of ethylene glycol derivatives such as polyethyleneglycol monomethyl ether, polyethylene glycol dimethyl ether andpolyethylene glycol monobutyl ether; propylene glycol derivatives suchas propylene glycol, dipropylene glycol, tripropylene glycol andpolypropylene glycol; polyethers such cyclodextrin and dextrin; esterssuch as methyl acetate and ethyl acetate; and N-alkyl pyrrolidone. Theamount of the organic solvent may be from 5 to 200 parts by weight, forexample, from 10 to 100 parts by weight, particularly from 20 to 80parts by weight, based on 100 parts by weight of the polymer.

If necessary, the aqueous dispersion liquid may contain additives suchas an organic acid, a crosslinking agent, another polymer, anotherwater-repellent agent and/or oil-repellent agent, a mothproofing agent,a flame retardant, an antistatic agent, a dye stabilizing agent, andanti-crease agent.

The crosslinking agent includes a blocked isocyanate compound, amelamine resin compound, a glyoxal resin compound, a urea resincompound, a polymer comprising a crosslinkable monomer (for example,N-methylol acrylamide, and a blocked material of 2-isocyanatoethylmethacrylate) as an essential polymerization unit. The blockedisocyanate compound and the melamine resin compound are preferable. Theblocked isocyanate compound is preferably a compound which is free of apolymerizable unsaturated group, and which has the structure wherein anisocyanate group of the polyisocyanate is blocked with a blocking agent.The melamine resin compound includes trimethylol melamine andhexamethylol melamine.

The aqueous dispersion liquid of the present invention can be preparedby emulsion-polymerizing the polymerizable compound in water containingthe organic solvent in the presence of a polymerization initiator andoptionally a surfactant to give the polymer emulsion (A), and thenadding the surfactant (B) and optionally water to the polymer emulsion.

A substrate to which the aqueous dispersion liquid is applied is atextile or a solid sheet. The substrate is preferably a sheet-shapedmaterial, for example, a fabric. The textile includes a fiber as such, ayarn made from the fiber, a fabric made from the fiber. The solid sheetis a sheet free of voids, unlike the fabric made of fiber.

The substrate may be a film, a fiber, a yarn, a woven fabric, a carpet,or a sheet made from a filament, fiber or yarn prepared from a naturalpolymer material, a modified natural polymer material or a synthesizedpolymer material.

The dispersion liquid according to the present invention can be appliedto the substrate preferably by coating, dipping, spraying, padding, rollcoating, or combination of these procedures. For example, a padding bathhaving the bath solid content of 0.1 to 10% by weight can be used. Thesubstrate is padded in the padding bath, and then excess liquid isusually removed by a squeezing roll to give the dry pickup amount (theweight of dry polymer on the substrate) of from 0.01 to 10% by weightbased on the weight of the substrate. Then, the treated substrate ispreferably heated at 100-200° C. depending on the necessity.

PREFERRED EMBODIMENTS OF THE INVENTION

Examples and Comparative Examples are shown hereinafter to illustratethe present invention in detail.

Properties are determined as follows:

Water- and Oil-Repellency

The polymer dispersion liquid is diluted with water to give a treatmentliquid having a solid content of 0.5% by weight. A polyester fabric isimmersed in the treatment liquid, squeezed with a mangle to give a wetpickup of 65%, dried at 100° C. for two minutes, heated at 160° C. forone minute, and then subjected to an evaluation of water- andoil-repellency.

The water-repellency is expressed by the water repellency No. (cf. thefollowing Table 1) determined by the spray method according to JIS(Japanese Industrial Standard) L-1092.

The oil-repellency is determined by dropping several drops of a testsolution shown in the following Table 2 according to AATCC-TM118 on twopositions of a surface of a test cloth and observing the penetrationstate of the drops after 30 seconds. The maximum point at which the testsolution exhibits no penetration is expressed by the oil-repellency.TABLE 1 Water repellency No. State 5 No wet on the surface 4 Slight weton the surface 3 Partial wet on the surface 2 Wet on the surface 1 Wetover the whole surface

TABLE 2 Surface tension Oil- (dyne/cm, repellency Test solution 25° C.)8 n-Heptane 20.0 7 n-Octane 21.8 6 n-Decane 23.5 5 n-Dodecane 25.0 4n-Tetradecane 26.7 3 n-Hexadecane 27.3 2 n-Hexadecane/Nujol mixturesolution 29.6 (35/65 by weight) 1 Nujol 31.2 0 Inferior to 1 —Wash Durability of Water- and Oil-Repellency

The wash according to JIS L-0217-103 is repeatedly conducted three timesand then the water- and oil-repellency (HL-3) is evaluated.

Storage Stability

After the aqueous dispersion (solid content: 30% by weight) is stored at40° C. for one month, the generation of precipitate is observed.

-   -   Good: No precipitation    -   Fair: Slight precipitation    -   Poor: Much precipitation        Impurity Stability

The aqueous dispersion is diluted with tap water to give a solid contentof 0.6% by weight. 0.03% by weight of a fixing agent for nylon is addedto the diluted dispersion and intimately stirred. The generation ofagglomerate is observed.

-   -   Good: No agglomerate generated    -   Fair: Slight agglomerate generated    -   Poor: Much agglomerate generated        Storage Stability

After the aqueous dispersion (solid content: 30% by weight) is stored at40° C. for one month, the generation of precipitate is observed.

-   -   Good: No precipitation    -   Fair: Slight precipitation    -   Poor: Much precipitation

EXAMPLE 1

Into a 1 L autoclave, C_(n)F_(2n+1)CH₂CH₂OCOCH═CH₂ (a mixture ofcompounds wherein n is 6, 8, 10, 12 and 14 (average of n: 8)) (150 g),stearyl acrylate (75 g), 3-chloro-2-hydroxypropyl methacrylate (3 g),pure water (300 g), tripropylene glycol (80 g), acetic acid (0.45 g),octadecyl trimethyl ammonium chloride (6 g) and polyoxyethylene laurylether (9 g) were charged and emulsified by ultrasonic wave at 60° C. for15 minutes with stirring. After the emulsification, n-dodecyl mercaptan(1.5 g) was added and vinyl chloride (45 g) was injected. Further,2,2′-azobis(2-amidinopropane) dihydrochloride (1.12 g) was added and thereaction was conducted at 60° C. for 5 hours to give an aqueous emulsionof the polymer. C₁₂H₂₅O—(C₂H₄O)_(a)—(C₃H₆O)_(b)—H (the average inpolyoxyethylene chain is 10 mol, and the average in polyoxypropylenechain is 4 mol) (3 g) was added to the aqueous polymer emulsion andstirred for 1 hour to give an aqueous dispersion liquid.

EXAMPLE 2

Into a 1 L autoclave, C_(n)F_(2n+1)CH₂CH₂OCOCH═CH₂ (a mixture ofcompounds wherein n is 6, 8, 10, 12 and 14 (average of n: 8)) (150 g),stearyl acrylate (37.5 g), 2-ethylhexyl methacrylate (37.5 g), diacetoneacrylamide (1.8 g), 3-chloro-2-hydroxypropyl methacrylate (1.2 g), purewater (300 g), dipropylene glycol monomethyl ether (70 g), acetic acid(0.45 g), di-hardened tallow alkyl dimethyl ammonium chloride (6 g) andpolyoxyethylene cetyl ether (9 g) were charged and emulsified byultrasonic wave at 60° C. for 15 minutes with stirring. After theemulsification, n-dodecyl mercaptan (1.5 g) was added and vinyl chloride(45 g) was injected. Further, 2,2′-azobis(2-amidinopropane)dihydrochloride (1.12 g) was added and the reaction was conducted at 60°C. for 5 hours to give an aqueous emulsion of the polymer.C₁₂H₂₅O—(C₂H₄O)_(a)—(C₃H₆O)_(b)—H (the average in polyoxyethylene chainis 14 mol, and the average in polyoxypropylene chain is 2 mol) (3 g) wasadded to the aqueous polymer emulsion and stirred for 1 hour to give anaqueous dispersion liquid.

EXAMPLE 3

Into a 1 L flask, C_(n)F_(2n+1)CH₂CH₂OCOCH═CH₂ (a mixture of compoundswherein n is 6, 8, 10, 12 and 14 (average of n: 8)) (100 g), stearylacrylate (50 g), N-methylol acrylamide (2 g), pure water (200 g),dipropylene glycol monomethyl ether (50 g), acetic acid (0.3 g),polyoxyethylene lauryl ether (4 g) and polyoxyethylene cetyl ether (10g) were charged and emulsified by ultrasonic wave at 60° C. for 15minutes with stirring. 2,2′-azobis(2-amidinopropane) dihydrochloride(0.75 g) was added and the reaction was conducted at 60° C. for 5 hoursto give an aqueous emulsion of the polymer.C₁₂H₂₅O—(C₂H₄O)_(a)—(C₃H₆O)_(b)—H (the average in polyoxyethylene chainis 10 mol, and the average in polyoxypropylene chain is 4 mol) (2 g) wasadded to the aqueous polymer emulsion and stirred for 1 hour to give anaqueous dispersion liquid.

EXAMPLE 4

Into a 1 L flask, C_(n)F_(2n+1)CH₂CH₂OCOCH═CH₂ (a mixture of compoundswherein n is 6, 8, 10, 12 and 14 (average of n: 8)) (100 g), stearylacrylate (50 g), diacetone acrylamide (2 g), pure water (200 g),dipropylene glycol monomethyl ether (50 g), acetic acid (0.3 g),di-hardened tallow alkyl dimethyl ammonium chloride (4 g) andpolyoxyethylene cetyl ether (8 g) were charged and emulsified byultrasonic wave at 60° C. for 15 minutes with stirring. Further,2,2′-azobis(2-amidinopropane) dihydrochloride (0.75 g) was added and thereaction was conducted at 60° C. for 5 hours to give an aqueous emulsionof the polymer. C₁₂H₂₅O—(C₂H₄O)_(a)—(C₃H₆O)_(b)—H (the average inpolyoxyethylene chain is 10 mol, and the average in polyoxypropylenechain is 4 mol) (1.6 g) was added to the aqueous polymer emulsion andstirred for 1 hour to give an aqueous dispersion liquid.

EXAMPLE 5

Into a 1 L flask, C_(n)F_(2n+1)CH₂CH₂OCOCH═CH₂ (a mixture of compoundswherein n is 6, 8, 10, 12 and 14 (average of n: 8)) (100 g), stearylacrylate (25 g), lauryl acrylate (25 g), N-methylol acrylamide (1.2 g),3-chloro-2-hydroxypropyl methacrylate (0.8 g), pure water (200 g),tripropylene glycol (50 g), ethylene glycol (10 g), acetic acid (0.3 g),octadecyl trimethyl ammonium chloride (4 g) and polyoxyethylene cetylether (8 g) were charged and emulsified by ultrasonic wave at 60° C. for15 minutes with stirring. 2,2′-azobis(2-amidinopropane) dihydrochloride(0.75 g) was added and the reaction was conducted at 60° C. for 5 hoursto give an aqueous emulsion of the polymer.C₁₂H₂₅O—(C₂H₄O)_(a)—(C₃H₆O)_(b)—H (the average in polyoxyethylene chainis 14 mol, and the average in polyoxypropylene chain is 2 mol) (1.6 g)was added to the aqueous polymer emulsion and stirred for 1 hour to givean aqueous dispersion liquid.

COMPARATIVE EXAMPLE 1

Used was an aqueous dispersion liquid prepared in the same manner as inExample 1 except that C₁₂H₂₅O—(C₂H₄O)_(a)—(C₃H₆O)_(b)—H (the average inpolyoxyethylene chain is 10 mol. and the average in polyoxypropylenechain is 4 mol) was not added to the aqueous emulsion.

COMPARATIVE EXAMPLE 2

Used was an aqueous dispersion liquid prepared in the same manner as inExample 2 except that C₁₆H₃₃O—(C₃H₆O)_(a)—(C₂H₄O)_(b)—H (the average inpolyoxyethylene chain is 10 mol, and the average in polyoxypropylenechain is 4 mol) was used instead of C₁₂H₂₅O—(C₂H₄O)_(a)—(C₃H₆O)_(b)—H(the average in polyoxyethylene chain is 14 mol, and the average inpolyoxypropylene chain is 2 mol) for the aqueous emulsion.

COMPARATIVE EXAMPLE 3

Used was an aqueous dispersion liquid prepared in the same manner as inExample 3 except that C₁₆H₃₃O—(C₃H₆O)_(a)—(C₂H₄O)_(b)—H (the average inpolyoxyethylene chain is 10 mol, and the average in polyoxypropylenechain is 4 mol) was used instead of C₁₂H₂₅O—(C₂H₄O)_(a)—(C₃H₆O)_(b)—H(the average in polyoxyethylene chain is 10 mol, and the average inpolyoxypropylene chain is 4 mol) for the aqueous emulsion.

COMPARATIVE EXAMPLE 4

Used was an aqueous dispersion liquid prepared in the same manner as inExample 4 except that C₁₆H₃₃O—(C₃H₆O)_(a)—(C₂H₄O)_(b)—H (the average inpolyoxyethylene chain is 20 mol, and the average in polyoxypropylenechain is 8 mol) was used instead of C₁₂H₂₅O—(C₂H₄O)_(a)—(C₃H₆O)_(b)—H(the average in polyoxyethylene chain is 10 mol, and the average inpolyoxypropylene chain is 4 mol) for the aqueous emulsion.

COMPARATIVE EXAMPLE 5

Used was an aqueous dispersion liquid prepared in the same manner as inExample 5 except that C₁₂H₂₅O—(C₂H₄O)_(a)—(C₃H₆O)_(b)—H (the average inpolyoxyethylene chain is 14 mol, and the average in polyoxypropylenechain is 2 mol) was not added to the aqueous emulsion. TABLE 3 Water-andoil-repellency Initial HL-3 Water Oil Water Oil Mechanical ImpurityStorage repellency repellency repellency repellency stability stabilitystability Example 1 5 6 5 4 Good Good Good Example 2 5 6 5 5 Good GoodGood Example 3 5 5 4 4 Good Good Fair Example 4 5 5 5 4 Good Good GoodExample 5 5 6 4 5 Good Good Good Comparative 5 6 5 4 Fair Fair FairExample 1 Comparative 5 6 5 5 Fair Fair Fair Example 2 Comparative 5 5 44 Poor Poor Poor Example 3 Comparative 5 5 4 4 Fair Fair Fair Example 4Comparative 5 5 4 4 Fair Poor Fair Example 5

EFFECTS OF THE INVENTION

The aqueous dispersion liquid of the present invention is excellent instability in the presence of impurity in a treatment bath, excellent instability against mechanical impact in the treatment bath, and canmaintain high water- and oil-repellency and high durability of water-and oil-repellency. The aqueous dispersion liquid does not haveprecipitation of particles and does not have the attachment of a polymerto a roll causing a soiled fabric.

1. An aqueous emulsion composition comprising: (A) an aqueous resinemulsion comprising a homopolymer or copolymer comprising at least onepolymerizable compound having a perfluoroalkyl or perf luoroalkenylgroup and an acrylate, methacrylate or alpha-substituted acrylate group,or a copolymer comprising said polymerizable compound and anothercompound copolymerizable therewith, and (B) a surfactant of the formula:R¹O—(CH₂CH₂O)_(p)—(R²O)_(q)—R³   (1) wherein R¹ is an alkyl group having1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, R²is an alkylene group having at least 3 carbon atoms, R³ is a hydrogenatom, an alkyl group having 1 to 22 carbon atoms or an alkenyl grouphaving 2 to 22 carbon atoms, p is the number of at least 2, q is thenumber of at least 1, and p and q are such numbers that the weight ratioof the polyoxyethylene block is from 5 to 80% by weight based on wholemolecule, wherein the surfactant (B) is added to the aqueous resinemulsion (A).
 2. The composition according to claim 1, wherein thealkylene group (R² group) in the surfactant (B) is propylene.
 3. Thecomposition according to claim 1, which further contains an antifoamingagent.
 4. A method of treating a substrate, which comprises using thecomposition according to claim
 1. 5. The method according to claim 4,which is for the purpose of imparting water- and oil-repellency to atextile.
 6. A substrate which is treated by the method according toclaim 4.